Materials Research.

2012; 15(6): 833-836 2012

DDOI: 10.1590/S1516-14392012005000108

Effect of Impurities on the Raman Scattering of 6H-SiC Crystals

Shenghuang Lin a*, Zhiming Chen a, Lianbi Li b, Chen Yang a

a
Department of Electronic Engineering, Xian University of Technology, Xian, 710048, PR, China
b
School of Science, Xian Polytechnic University, Xian, 710043, PR, China

Received: November 7, 2011; Revised: May 14, 2012

Raman spectroscopy was applied to different-impurities-doped 6H-SiC crystals. It had been found
that the first-order Raman spectra of N-, Al- and B-doped 6H-SiC were shifted to higher frequency
when comparing with undoped samples. However, the first-order Raman spectra of V-doped sample
was shifted to lower frequency, revealing that there existed low free carrier concentration, which might
be induced by the deep energy level effect of V impurity. Meanwhile, the second-order Raman spectra
are independent of polytype and impurity type.

Keywords: Raman scattering, 6H-SiC, impurity

1. Introduction
Silicon carbide (SiC), one of the oldest known
semiconductor materials, has received special attention
in recent years because of its suitability for electronic and
optoelectronic devices operating under high temperature,
high power, high frequency, and/or strong radiation
conditions1-5. As a perfect wide band gap semiconductor,
SiC is an insulator whose intrinsic resistivity can be up
to ~3.75 1021 cm. Incorporation of foreign dopants
can create impurities energy levels relatively close to the
conduction or valence band edges, which offers a bridge
to easily excite electron (donor) or hole (acceptor) into the
bands. N- or p-type SiC crystals can be achieved by doping
different impurities, and the conductivity is proportional
to the doping concentration when the carrier mobility is
regarded as a constant. The shallower the dopant energy
levels, the lower the temperature where the full dopant
concentration becomes active. Nitrogen (N) or phosphorus
(P) for n-type, aluminum (Al) or boron (B) for p-type and
vanadium (V) for semi-insulating type, are often chosen for
SiC doping. These impurities-doped SiC crystals are widely
applicable. Therefore, characterization of them is essential
for the development of SiC materials and devices.
In addition to other techniques, including atomic force
microscopy (AFM) and scanning electron microscopy
(SEM), Raman spectroscopy is becoming an increasingly
common analysis method. It offers fast and contact-free
measurements with easy sample preparation. Raman
spectroscopy is a vibrational spectroscopy method that is
based on the analysis of inelastically scattered light. The
incident photons scatter of molecular vibrations (e.g.,bending
and rotational vibrations) or, in the case of crystals, off
phonons (e.g., different modesoflatticevibration). As a
result, specific spectral peak shifts occur, providing highly
sensitive measurements of the material. The spectra consist
of peaks that are unique in their position, shape and intensity.
Usually, lasers are used as monochromatic excitation sources
*e-mail: shenghuanglin@163.com
and the so-called Raman shift, i.e., the energy loss (or gain)
of the scattered light, is given.
Now, Raman spectroscopy has been applied to SiC material
for characterizations of polytypes6-8, stacking faults9, stress10
and doping7,11,12. In addition, it also has been employed to SiC
crystals for investigating the properties in the vicinity and in
the center of micropipes13. Especially, the Raman scattering
on N-doped SiC has been reported in many papers7,14-17. In this
case, the significant changes could be observed in the shape
and position of the A1 longitudinal optical (LO) phonon as
a function of doping concentration. Meanwhile, the Raman
scattering has also been employed to characterize aluminum
(Al) doped 6H-SiC17,18, the latter of which is focusing on the
temperature-dependent properties. However, the effects of Al,
boron (B) and vanadium (V) doping on Raman scattering are
still rarely reported. Meanwhile, the difference observed from
Raman scattering among these different-impurities-doped
SiC crystals has not been investigated yet. In this paper, we
investigate the effect of these impurities on Raman scattering at
room temperature. It had been found that the Raman peaks of
Al-, B-, V- and N-doped 6H-SiC shift to different frequencies,
especially the peak at ~964 cm1. Then the difference among
them is discussed.
2. Experimental
SiC single crystals were grown in a conventional
physical vapor transport (PVT) setup2. Nitrogen (N) doping
was performed by mixing nitrogen gas to the argon growth
atmosphere. Aluminum (Al) and Boron (B) doping were
achieved by the foreign impurities absorbed in the graphite
crucible. Vanadium (V) doping was completed by mixing
vanadium carbide (VC) to the high-purity SiC powder. The
Raman spectra were measured by Renishaw inVia Raman
spectrometer at room temperature using the Ar+ laser of a
25mW at 514 nm as the excitation source. All the spectral
scans were performed in the range of 100~2000 cm1. The
834 Shenghuang et al. Materials Research

accuracy of the frequency measurement was better than
1.0cm1.
3. Results and Discussion
As we know, there are a large number of SiC polytypes
for which the stacking sequences of double atomic planes
of Si-C along the c-direction are different. The simplest
polytype with the shortest period is the 3C polytype (-type)
which has a zincblende (cubic) structure. But one of the
Figure1. The first-order Raman spectra of different-impurities-
doped 6H-SiC samples.
two most popular polytypes is 6H polytype, which has a
wurtzitic structure with C6v 4
space group. And the group
theory analysis predicts that the Raman active modes are of
A1 (LO) and E1 (TO) symmetry. Due to the optical branches
of A1 and E1 symmetry phonon modes being both Raman
and IR active, they split into longitudinal and transverse
branches. As the same shown in Figure1, which reveals
the first-order Raman spectra of different-impurities-doped
6H-SiC samples. It can be seen that there exist four typical
peaks for FTA, FLA, FTO and FLO modes, respectively.
As for the undoped 6H-SiC samples, it had been reported
that these typical peaks were at 150 (FTA), 504 (FLA),
765(FTO), 787 (FTO) and 964 (FLO)cm1, respectively6,17.
But for impurities-doped 6H-SiC samples, the typical peaks
will be quite different.
Figure2 shows the local amplification corresponding to
Figure1 in the range of 720-1000cm1. By a combination
of Figure2 and Table1, it could be found that almost all the
Raman peaks shifted to higher frequency except for V-doped
sample. Especially for the peak of A1 mode at~964cm1,
it had been revealed that this peak would shift to higher
frequency with the increase of carrier concentration 17.
However, the Raman peak for V-doped sample shifted to
lower frequency when comparing with undoped sample. It
implied that the carrier concentration in V-doped 6H-SiC
was lower than that of undoped sample, revealing the
conventional residual impurity N had been compensated by
the deep energy level impurity V. Meanwhile, the ionization

Figure2. Local amplification for Figure1 in the range of 720-1000 cm1.

Table1. Phonon modes of the different-impurities-doped 6H-SiC observed by Raman spectroscope.

Frequency (cm1)
FTA FLA FTO FTO LOPC
Reference (undoped) 150 504 766 787 964
N-doped 150.731 505.976 766.612 789.352 965.106
Al-doped 150.982 506.477 766.109 789.352 964.973
B-doped 150.355 505.579 766.335 789.352 967.405
V-doped 148.516 501.463 765.132 785.682 963.769
x 0.33 (6H) 0.67 (6H) 1 (6H) 0.33 (6H) 0 (6H)
2012; 15(6) Effect of Impurities on the Raman Scattering of 6H-SiC Crystals
energy of V in SiC is so large that there are only few free
carriers contributing to the conductivity. Therefore, the
Raman frequency of V-doped SiC showed red shift due to
its low carrier concentration. In order to investigate the real
mechanism of this phenomenon, the principle for Raman
spectroscopy is reviewed.
As we know, the spectral shape depends on the amount
of plasmon damping due to carrier scattering. The line shape
of the LO phonon can be written as6,11
1 (1)
I ( ) = SA( ) Im[ ] improve the value of P, and hence enhance the coupling
( )
where S is a proportionality constant, the Raman shift,
() the dielectric function, and A() is given by
2C T2 [ 2P (T2 2 ) 2 ( 2 2 2P )]
A( ) = 1 +
C 2 T4 2P [ ( 2L T2 ) + ( 2P 2 2 )] + 2 ( 2 + 2 ) (2)
+ because there is only one phonon being involved. But the
2L T2
Here, L and T represent the longitudinal and transverse
optical phonon frequencies, respectively, the plasmon
dampening constant, the phonon dampening constant,
Figure3. Second-order Raman spectra of different-impurities-
doped 6H-SiC.
Figure4. First-order Raman spectra of 6H-, 4H- and 15R-SiC samples.
835
a n d = 2P [(T2 2 )2 + ( )2 ] + 2 ( 2L T2 )( 2 + 2 ),
a n d C t h e s o - c a l l e d Fa u s t - H e n r y c o e ffi c i e n t .
The dielectric function () can be expressed as
2 2 2P
( ) = 1 + 2 L 2 T , which contains
T i ( + i )
contribution from phonon and plasmon. And the plasmon
frequency P = (4ne2/m)1/2, which is related to optical
dielectric constant (), electron effective mass (meff) and
carrier density (n). The increase of the carrier density will
interaction between phonons and plasmon. Then the LO
phonon frequency would increase and reveal blue shift with
the increase of carrier concentration. In stead, the Raman
frequency would be shifted to lower wavenumber.
It is well known that the first-order Raman spectra only
represent the phonons in the first Brillouin zone ( point)
second-order Raman spectra show the information about
the whole Brillouin zone due to two phonons participating.
Figure3 shows the second-order Raman spectra of different-
impurities-doped 6H-SiC. It can be seen that the Raman peaks
are labelled a (1472cm1), b(1513cm1), c(1526cm1),
d(1537cm1), e (1582cm1), f (1617cm1),g(1655cm1),
h (1688cm1), i (1712cm1), j (1931cm1). According to
the selective rules for secondorder scattering in hexagonal
materials19, the peaks marked as a, b, c, d, e and f are assigned
to the two-phonon Raman scattering. However, there is no
significant difference can be found among these different
impurities doped 6H-SiC in the second-order Raman spectra.
Namely, the doping concentrations have no influence on the
second- order Raman scattering of SiC crystals.
In addition, the first- and second-order Raman scattering
are also investigated in this paper. The first-order Raman
spectra of 6H-, 4H- and 15R-SiC crystals are shown in
Figure4. The difference among these polytypes can be easily
distinguished by the feature peaks of FTA mode, such as
6H- at ~151cm1, 4H- at ~203cm1 and 15R- at ~171cm1.
However, as for the N-doped 6H-, 4H- and 15R-SiC crystals,
no Raman shifts can be observed in the second-order Raman
spectra (see Figure5). Therefore, the second-order Raman
scattering is independent of polytypes.
Figure5. Second-order Raman spectra of 6H-, 4H- and 15R-SiC
samples.
836 Shenghuang et al.
4. Conclusions
In summary, the SiC polytypes have significant effects
on the first-order Raman scattering due to the existence of
the folded modes. The Raman frequency and intensity of
the observed peaks are polytype and doing concentration
dependent. It had also been found that the Raman peaks of
N-, Al- and B-doped 6H-SiC shift to high frequency, but
that of V-doped sample shift to low frequency. The possible
reason for this phenomenon is that the shallow energy
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